Catalytic processes hydrogenation

A significant coverage with respect to Ha can be attained on some noble metals (Pt, Pd, Rh). Chemisorbed hydrogen plays a key role in many electro catalytic processes (- hydrogen evolution, - electrocatalysis, electrohydrogenation). 

Dual Function Catalytic Processes. Dual-function catalytic processes use an acidic oxide support, such as alumina, loaded with a metal such as Pt to isomerize the xylenes as weH as convert EB to xylenes. These catalysts promote carbonium ion-type reactions as weH as hydrogenation—dehydrogenation. In the mechanism for the conversion of EB to xylenes shown, EB is converted to xylenes... 

Any of the medium heat-value gases that consist of carbon monoxide and hydrogen (often called synthesis gas) can be converted to high heat-value gas by methanation (22), a low temperature catalytic process that combines carbon monoxide and hydrogen to form methane and water. 

Dehydrogenation of isobutane to isobutylene is highly endothermic and the reactions are conducted at high temperatures (535—650°C) so the fuel consumption is sizeable. Eor the catalytic processes, the product separation section requires a compressor to facHitate the separation of hydrogen, methane, and other light hydrocarbons from-the paraffinic raw material and the olefinic product. An exceHent overview of butylenes is avaHable (81). 

Cost. The catalytically active component(s) in many supported catalysts are expensive metals. By using a catalyst in which the active component is but a very small fraction of the weight of the total catalyst, lower costs can be achieved. As an example, hydrogenation of an aromatic nucleus requires the use of rhenium, rhodium, or mthenium. This can be accomplished with as fittie as 0.5 wt % of the metal finely dispersed on alumina or activated carbon. Furthermore, it is almost always easier to recover the metal from a spent supported catalyst bed than to attempt to separate a finely divided metal from a liquid product stream. If recovery is efficient, the actual cost of the catalyst is the time value of the cost of the metal less processing expenses, assuming a nondeclining market value for the metal. Precious metals used in catalytic processes are often leased. 

Hydrocarbons from Synthesis Gas and Methanol. Two very important catalytic processes in which hydrocarbons are formed from synthesis gas are the Sasol Eischer-Tropsch process, in which carbon monoxide and hydrogen obtained from coal gasification are converted to gasoline and other products over an iron catalyst, and the Mobil MTG process, which converts methanol to gasoline range hydrocarbons using ZSM-5-type 2eohte catalysts. 

Chlorine atoms obtained from the dissociation of chlorine molecules by thermal, photochemical, or chemically initiated processes react with a methane molecule to form hydrogen chloride and a methyl-free radical. The methyl radical reacts with an undissociated chlorine molecule to give methyl chloride and a new chlorine radical necessary to continue the reaction. Other more highly chlorinated products are formed in a similar manner. Chain terrnination may proceed by way of several of the examples cited in equations 6, 7, and 8. The initial radical-producing catalytic process is inhibited by oxygen to an extent that only a few ppm of oxygen can drastically decrease the reaction rate. In some commercial processes, small amounts of air are dehberately added to inhibit chlorination beyond the monochloro stage. 

Additional catalytic processes. Nitrobenzene is hydrogenated to aniline (U.S. Patent 2,891,094). Melamine and isophthalouitrile are produced in catalytic fluidized-bed readers. Badger has announced a... 

A route to phenol has been developed starting from cyclohexane, which is first oxidised to a mixture of cyclohexanol and cyclohexanone. In one process the oxidation is carried out in the liquid phase using cobalt naphthenate as catalyst. The cyclohexanone present may be converted to cyclohexanol, in this case the desired intermediate, by catalytic hydrogenation. The cyclohexanol is converted to phenol by a catalytic process using selenium or with palladium on charcoal. The hydrogen produced in this process may be used in the conversion of cyclohexanone to cyclohexanol. It also may be used in the conversion of benzene to cyclohexane in processes where benzene is used as the precursor of the cyclohexane. 

Hydrogen cyanide, mp —13.3° bp 25.7°, is an extremely poisonous compound of very high dielectric constant (p. 55). It is miscible with H2O, EtOH and Et20. In aqueous solution it is an even weaker acid than HE, the dissociation constant Ka being 7.2 x 10 ° at 25°C. It was formerly produced industrially by acidifying NaCN or Ca(CN)2 but the most modem catalytic processes are based on direct reaction between... 

Catalytic processes frequently require more than a single chemical function, and these bifunctional or polyfunctional materials innst be prepared in away to assure effective communication among the various constitnents. For example, naphtha reforming requires both an acidic function for isomerization and alkylation and a hydrogenation function for aromati-zation and saturation. The acidic function is often a promoted porous metal oxide (e.g., alumina) with a noble metal (e.g., platinum) deposited on its surface to provide the hydrogenation sites. To avoid separation problems, it is not unusual to attach homogeneous catalysts and even enzymes to solid surfaces for use in flow reactors. Although this technique works well in some environmental catalytic systems, such attachment sometimes modifies the catalytic specifici-... 

Other important catalytic processes are those directed toward improving the product quality through hydrotreatment. These processes use heterogeneous hydrogenation catalysts. 

An early success story in the field of catalytic asymmetric synthesis is the Monsanto Process for the commercial synthesis of l-DOPA (4) (see Scheme 1), a rare amino acid that is effective in the treatment of Parkinson s disease.57 The Monsanto Process, the first commercialized catalytic asymmetric synthesis employing a chiral transition metal complex, was introduced by W. S. Knowles and coworkers and has been in operation since 1974. This large-scale process for the synthesis of l-DOPA (4) is based on catalytic asymmetric hydrogenation, and its development can be... 

Hydrogenation of unsaturated fats and fatty oils is one of the oldest heterogeneous catalytic processes of industrial significance, and is carried out exclusively by gas-liquid-particle operation, the vaporization of the fats being impracticable. Stirred-slurry operation is the normal mode of operation, the suspended catalyst being finely divided by Raney nickel (B2). 

---